Effects of Al Substitution for Fe in Na₅FeSi₄O₁₂ (5.1.8) Glasses: Structure and Crystallization

Raine Antonio; John Bussey; Malin C.  J. Dixon Wilkins; Daniel Neuville; Laurent Cormier; John McCloy

doi:10.52825/glass-europe.v2i.2341

Authors

Raine Antonio Washington State University https://orcid.org/0009-0006-3429-7975
John Bussey Washington State University https://orcid.org/0000-0002-3760-5914
Malin C. J. Dixon Wilkins Washington State University https://orcid.org/0000-0003-1520-7672
Daniel Neuville Université Paris Cité https://orcid.org/0000-0002-8487-5001
Laurent Cormier Sorbonne Université https://orcid.org/0000-0002-3554-0707
John McCloy Washington State University https://orcid.org/0000-0001-7476-7771

DOI:

https://doi.org/10.52825/glass-europe.v2i.2341

Keywords:

Na₅FeSi₄O₁₂, Na₅MSi₄O₁₂, Crystallized Glass, Glass Structure, Raman Spectroscopy, XANES

Abstract

In this study, the effects of substituting Al for Fe in 5Na₂O∙(Al₂O₃)_x∙(Fe₂O₃)_1-x∙8SiO₂ glass, x=0 to 1, and Na₅Al_xFe_1-xSi₄O₁₂(5.1.8) crystal, were investigated using thermal analysis, Fe K-edge X-ray absorption, X-ray diffraction, Raman spectroscopy, and Electron Probe Microanalysis. In both glass and crystallized glass, nearly all the Fe was tetrahedrally coordinated Fe³⁺, as expected from the high concentration of Na₂O. The substitution of Al for Fe in the glasses caused the glass transition temperature to increase as polymerization increased, as evidenced by Raman, likely due to both field strength differences of Al vs Fe and a small amount of Fe²⁺ network modifier present with Fe. After heat treatment at 700 °C for 24 hours, the glasses had crystallized, forming Na₂SiO₃ and NaAlSiO₄ in compositions with high Al concentrations and the 5.1.8 crystal in compositions with high Fe concentrations. Through electron microprobe, it was determined that <0.04 formula unit Al incorporated into the 5.1.8 crystal, i.e. Na₅Fe_0.96Al_0.04Si₄O₁₂. The 5.1.8 crystal only formed when Fe concentration was higher than Al in the starting glass.

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Effects of Al Substitution for Fe in Na₅FeSi₄O₁₂ (5.1.8) Glasses: Structure and Crystallization

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